Patent DE-10127171-A1 (DE)
Title: New metal-organic monoacyl-alkyl-phosphine compounds are used for production of acyl-phosphine oxide or acyl-phosphine sulfide photoinitiators for use in light-curable compositions, e.g. paint, printing ink, adhesives
Inventor: WOLF JEAN-PIERRE
IPC: C09D11/101
Filed: 2001-06-05
Abstract: New metal-organic monoacyl-alkyl-phosphines are claimed. Metal-organic compounds of formula (I) are new. Ar = formula (IV), or cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an -, S- or N-containing 5- or 6-membered heterocyclic ring (all optionally substituted with halogen, 1-4C alkyl and/or 1-4C alkoxy);  R1, R2 = 1-20C alkyl, OR11, CF3 or halogen and R3-R5 = H, 1-20C alkyl, OR11 or halogen, or any two of these groups (R1-R5) may form a 1-20C alkylene bridge, optionally containing -O-, -S- or -NR14-;  R6 = 1-24C alkyl (optionally substituted with cycloalkenyl, phenyl, CN, COR11, COOR11, CON(R14)2, OCOR11, OCOOR11, -N(R14)CON(R14)-, OCONR14, -N(R14)COOR11, cycloalkyl, halogen, OR11, SR11, NR12R13 or oxiranyl), 2-24C alkyl with non-adjacent, in-chain O, S and/or NR14 group(s) (optionally substituted with phenyl, OR11, SR11, NR12R13, CN, COR11, COOR11, CON(R14)2 and/or oxiranyl), 2-24C alkyl with non-adjacent, in-chain O, S or NR14 (optionally substituted with OR11, SR11 or NR12R13), 5-24C cycloalkenyl (optionally with non-adjacent O, S or NR14 and optionally substituted withOR11, SR11 or NR12R13), 1-24C aralkyl (optionally ring-substituted with 1-12C alkyl, 1-12C alkoxy or halogen), 4-24C cycloalkyl (optionally with non-adjacent O, S and/or NR14 and optionally substituted with OR11, SR11 or NR12R13), 8-24C arylcycloalkyl or 8-24C arylcycloalkenyl;  R11 = H, 1-20C alkyl, 2-20C alkenyl, 3-8C cycloalkyl, phenyl, benzyl, or 2-20C alkyl with in-chain O or S atom(s) and optionally substituted with OH and/or SH; R12, R13 = H, 1-20C alkyl, 3-8C cycloalkyl, phenyl, benzyl or 2-20C alkyl with in-chain O atom(s) and optionally substituted with OH and/or SH, or R12 and R13 together may form a 3-5C alkylene group (optionally with in-chain O, S or NR14);  R14 = H, phenyl, 1-12C alkyl, or 2-12C alkyl with in-chain O or S and optionally substituted with OH and/or SH;  M = H, lithium, sodium or potassium. Independent claims are also included for: (a) compounds of formula (II) and (III); (b) the selective production of (I) by reaction of an acyl halide of formula Ar-CO-X (IV) with a dimetalated organophosphine R6-P(M1)2 (V) in a mol ratio of 1:1, followed by hydrolysis if (I) with M = H is required; (c) the production of (II) by reaction of (IV) with (V) as above, reaction of the product with a different acyl halide (Y1-CO-X) (IVa) and oxidation or sulfidation of the phosphine (for A = O or S); (d) the production of (II) (with A = O and x = 1) by reaction of (I) with phosgene to give the phosphine chloride, reaction with an alcohol to give Ar-CO-P(R6)(OR) and reaction with acyl halide (IVa); (e) the production of (III) by reaction of (IV) with (V), reaction of the product with a compound of formula Z1-X (VI) or Z1-X' (VI') and oxidation or sulfidation as above; (f) the production of (III) by reaction of (IV) with an asymmetrical phosphine R6-P(Z1)-H (VII) in presence of an organolithium compound to give an acylphosphine, followed by oxidation or sulfidation; (g) the production of (III) by reaction of (I) with phosgene, reaction of the phosphine chloride with an alcohol (see above) and reaction with a halide Z1-X (in methods c-h); (h) photo-hardenable compositions containing photo-polymerizable unsaturated compounds plus compound(s) (II) and/or (III) as photoinitiators; (i) the photopolymerization of non-volatile, mono-, oligo- or poly-meric compounds with ethylenic double bond(s) by irradiating the compositions (i) with light in the 200-600 nm range; (j) substrates coated with the compositions; (k) the photographic production of relief images by exposing the coated substrates to light to form an image and then removing the unexposed parts with a solvent. A = O or S;  x = 0 or 1;  Y1 = 1-18C alkyl (optionally substituted with phenyl(s)), 1-18C haloalkyl, 2-18C alkyl with in-chain O or S (optionally substituted with OH and/or SH), 3-18C cycloalkyl (optionally substituted with 1-10C alkyl, OR11, CF3 or halogen), 2-18C alkenyl, OR11, NR12R13, a group of formula (IV), -Y2-CO-P(R6)(A)x-CO-Ar, or cyclopentyl, cyclohexyl, naphthyl etc. (see other groups as listed above for Ar), with the proviso that Y1 and Ar are not identical;  Y2 = direct bond or various (cyclo)alk(en)ylene or arylene groups; Z1 = 1-24C alkyl (optionally substituted with OR15, SR15, NR16R17, phenyl, halogen, CN, -NCA, oxiranyl, -C(A)R18, -C(A)-OR18 and/or -C(A1)N(R18)2), 2-24C alkyl with in-chain O, S or NR14 (optionally substituted as for 1-24C alkyl), 1-24C alkoxy (optionally substituted with phenyl, CN, NCA, oxiranyl etc. (see 1-24C alkyl), -C(A)-OR11, -C(A1)-NR16R17, -C(A)-OR11a, -C(A1)-N(R18a)(R18b), 3-24C cycloalkyl (optionally substituted), 2-24C alkenyl (optionally substituted), 3-24C cycloalkenyl, or (all optionally substituted) phenyl, phenyl linked via -Z3-, pyridyl, pyrimidyl, s-triazinyl, phthalimidyl, anthraquinonyl (or analogous groups with one CO group replaced by S, CH2, CO, NR14 or a direct bond), benzophenone groups, -Z2-P(A)x(R6)-COAr, polysiloxanyl, polysilanyl, arylthio or benzylthio, or 1-24C alkylthio (optionally with in-chain O or S or optionally substituted with OR15, SR15 or halogen);  A1 = O, S or NR18a;  Z2 = 1-24C alkylene, 2-24C alkylene or alkenylene, 3-24C cycloalkylene or cycloalkenylene (all optionally with in-chain hetero atoms as above and optionally substituted), phenylene, -Phe-Z5-Phe-, -Z6-Phe-Z7-, or a polysiloxane or polysilane residue;  Phe = phenylene;  Z3 = CH2, CHOH, CHCH3 or C(CH3)2;  Z5 = S, O, CH2, CHCH3, C(CH3)2, C(CF3)2, SO, SO2 or CO;  Z6, Z7 = CH2, CHCH3 or C(CH3)2; R11a = optionally substituted alkyl, alkoxy, alkenyl, alkynyl, cycloalkenyl, aralkyl or arylcycloalkyl etc.;  R15 = as for R11, or -C(A)-R18, -C(A)-OR18 or -C(A1)-N(R18)2;  R16, R17 = as for R12, or -C(A)-R18, -C(A)-OR18 or -C(A1)-N(R18)2;  R18, R18a, R18b = H or various hydrocarbyl groups (optionally modified and/or substituted); X = Cl or Br;  M1 = Li, Na or K;  X' = -NCA, -NCNZ1, oxiranyl or -CHO.